Process for the catalytic conversion of methane or natural gas to syngas or a mixture of carbon monoxide and hydrogen

A process for catalytic conversion of methane or natural gas to syngas or a mixture of carbon monoxide and hydrogen using a supported catalyst comprising a layer of alkaline earth metal oxide on an inert refractory solid support, said catalyst containing oxides of nickel and cobalt, with or without noble metals, represented by the formula:

• AaCobNiOc(X)MOd(4)/S
• wherein, A is noble metal element selected from the group consisting of Ru, Rh, Pd, Pt, Ir, Os and a mixture thereof, Co is cobalt, Ni is nickel, O is oxygen, M is alkaline earth metal selected from the group consisting of Be, Mg, and a mixture thereof, a is A/Ni mole ratio in the range of 0 to about 0.1;
• b is a Co/Ni mole ratio in the range of about 0.01 to about 2.0, c is number of oxygen atoms needed to fulfill the valence requirement of AaCobNi, d is number of oxygen atoms required to fulfill the valence requirement of M, S is the support for said catalyst selected from the group of sintered porous refractory inert solids consisting of alumina, silica, silica-alumina, silicon carbide, zirconia, hafnia and a mixture thereof said support having a surface area in the range of about 0.002 m2g−1 to about 5.0 m2g−1, y is weight percent loading of MOd precoated on said support in the range of about 0.3 wt % to about 30 wt %, and x is wt % loading of AaCobNiOc deposited on the precoated support in the range of about 0.3 wt. % to about 30 wt. %, which comprises:
• a) providing a feed stock mixture at ambient temperature by mixing oxygen with carbon dioxide and with methane or natural gas, wherein said feed stock mixture has mole ratio of CH4/CO2 from 3 to 24.8;
• b) preheating water or steam and the feed stock mixture of step (a) to a temperature between about 600° C. and about 900° C,
• c) admixing said preheated water or steam with said preheated feed stock mixture to create admixture feed, wherein said preheated water or steam is a main reactant;
• d) passing continuously the resulting admixture feed of step (c)
• over said supported catalyst in a fixed bed reactor operated adiabatically or non-adiabatically, and maintaining mole ratio of organic carbon to oxygen and steam in said admixture feed in step (c) between about 1.8 and about 2.8 and between about 1.1 and about 25, respectively, a gas hourly space velocity of said admixture feed between about 2000 cm3g−1h−1 and about 200,000 cm3g−1h−1, a reaction temperature between about 650° C. and about 925° C. and a pressure between about 1 atm and about 50 atm, such that an effluent is produced containing carbon monoxide and hydrogen, said effluent having a mole ratio of hydrogen to carbon monoxide of between about 1.5 and about 3.0 and containing less than about 4 mole % of methane or natural gas, wherein the catalytic conversion of methane or natural gas has 100 percent for both, CO and H2, and wherein in said fixed bed reactor there is a coupling of exothermic oxidative conversion of methane by O2 and endothermic reforming of methane by both steam and CO2 due to simultaneous occurence of these exothermic and endothermic reactions, with a net heat of reactions in the overall process, Hr, of between about −10 kcal per mole of organic carbon converted and about +15 kcal per mole of organic carbon converted.